Epoxy curing agents and method for making them

ABSTRACT

A new class of epoxy curing agents has been discovered that utilizes the monomer of (a) urea-formaldehyde, (b) phenol modified urea-formaldehyde, or (c) thiourea-formaldehyde as the center of a polyamine molecule. The ether monomers are reacted with conventional aliphatic, cycloaliphatic, and aromatic polyamines to split off alcohol and water-yielding urea-formaldehyde etc., polyamine epoxy curing agents.

This application is a continuation-in-part of application Ser. No. 396,319, filed July 8, 1982; now U.S. Pat. No. 4,490,510.

This invention relates to novel compounds useful as epoxy curing agents, to a method for making these new compounds.

A new class of epoxy curing agents has been discovered that utilizes the structure of urea-formaldehyde and also the structure of phenol-modified urea-formaldehyde as the center of a polyamine molecule. The amine groups are arranged around the urea-formaldehyde center in a radial fashion.

This may be represented as: ##STR1## where X¹ is ##STR2## and X² is either identical to X¹ or is ##STR3## R¹, R², R³, and R⁴ are defined below.

This structure has a low amount of steric hindrance; that is, structure of the molecule allows the most space between its components. This provides easy access for an epoxy molecule to react with these widely spaced amine groups.

The structures of these new compounds give a high degree of cross linking when reacted with epoxy resins and, therefore, contribute to the toughness and strength of the cured amine-epoxy resin.

Another advantage of incorporation of the urea-formaldehyde structure in the polyamine curing agent is that the curing agent is water-white in color, and so the subsequently cured amine-epoxy resin can be water-white. Urea-formaldehyde resins themselves are intrinsically colorless and resist becoming yellowish, and this same resistance to yellowing can be incorporated in the urea-formaldehyde polyamine structure.

The phenol-modified urea-formaldehyde resin have some yellowness, but are quite light.

Both the urea-formaldehyde polyamines and phenol-modified urea-formaldehyde polyamines can be low in cost, because urea, formaldehyde, and phenol are low-cost raw materials, and so are many of the polyamines.

Success in manufacturing these urea-formaldehyde polyamine curing agents depends, in part, on employing a process of urea-formaldehyde synthesis that produces largely monomeric urea-formaldehyde ether molecules.

One successful method of making urea-formaldehyde ether monomers is to react urea and paraformaldehyde in a low-molecular-weight alcohol, such as methanol at a ratio of urea molecules to formaldehyde molecules of one to four. This results in the following general structure: ##STR4##

Here, R is a methyl, ethyl, propyl, or butyl radical. When R is a methyl radical the compound is N,N'-bis(methoxymethyl) uron monomer; generalized the compound is N,N'-bis(alkoxy methyl) uron monomer (see U.S. Pat. No. 3,309,341).

Once this monomeric urea-formaldehyde ether molecule has been synthesized, it can be reacted directly with any of a number of polyamines including those that are presently utilized in the manufacture of amine curing agents. In this reaction about two to about four moles of the polyamine are reacted with each mole of the monomeric urea-formaldehyde ether molecule, taking care not to use two little amine such as would result in gelling.

A fundamental discovery of this invention is the discovery that polyamines or monoamines split the ether groups of the above urea-formaldehyde molecule. Then, one of the amine groups of the polyamine forms a carbon-nitrogen bond at the side of the ether splitting, giving off the reaction products of alcohol and water. For example: ##STR5##

R⁵ is a lower alkyl radical, having one to four carbon atoms.

This ease of splitting of these ether groups is somewhat surprising, because I had earlier found that the corresponding ether groups in a melamine formaldehyde resin are not split, under the same conditions.

As stated above, X¹ may be generalized as ##STR6## The following table shows the complete grouping of these radicals that can be R¹.

                                      CHART FOR R.sup.1                            __________________________________________________________________________     Name of Polyamine                                                              Used to React with                                                             U-F Monomer, etc.           R.sup.1                                            __________________________________________________________________________     (a)                                                                               diethylene triamine                                                                                      ##STR7##                                          (b)                                                                               triethylene tetramine                                                                                    ##STR8##                                          (c)                                                                               hexamethylene diamine    CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub                                 .2                                                 (d)                                                                               polyoxypropylene diamines                                                                               CH(CH.sub.3)CH.sub.2[OCH.sub.2CH(CH.sub.3)]                                    .sub.X                                                X = 2.6 has M.W. (molecular weight) of 230 approx.                             X = 5.6 has M.W. (molecular weight) of 400 approx.                             Commercial Name:                                                               Jeffamine D-230                                                                Jeffamine D-400                                                                Texaco Chemical Co.                                                         (e)                                                                               polyoxypropylene triamine                                                                                ##STR9##                                             X + Y + Z = 5.3                                                                M.W. of 400                                                                    Commercial Name:                                                               Jeffamine T-403                                                             (f)                                                                               poly (oxyethylene) diamine                                                                               ##STR10##                                            b = 13.5                                                                       a + c = 3.5                                                                    M.W. of 600                                                                    Commercial Name:                                                               Jeffamine ED diamine                                                        (g)                                                                               trimethyl hexamethylene diamine                                                                          ##STR11##                                         (h)                                                                               Naminoethyl piperazine                                                                                   ##STR12##                                         (i)                                                                               1,5 aminomethyl pentane diamine                                                                          ##STR13##                                         (j)                                                                               2 methyl pentamethylene diamine                                                                          ##STR14##                                         (k)                                                                               isophorone diamine                                                                                       ##STR15##                                         (l)                                                                               1,2-diamine cyclohexane                                                                                  ##STR16##                                         (m)                                                                               xylene diamine                                                                                           ##STR17##                                         (n)                                                                               2,4-bis(p-amino benzyl) aniline an aromatic polyamine                                                    ##STR18##                                         (o)                                                                               BABA (du Pont), mixture principally of methylene dianiline and                                           ##STR19##                                            2,4 bis(p-amino benzyl) aniline                                                                          ##STR20##                                         (p)                                                                               oleyl diamine            CH.sub.2CH.sub.2CH.sub.2                           __________________________________________________________________________

For all of the amines (a) through (o) in the above table, R² and R³ are both H. For the oleyl diamine, amine (p), either R² or R³, but not both, is C₁₈ H₃₅ and the other one is again H.

In the formula ##STR21## X¹ is as defined above, while X² may either be identical to X¹ or may be ##STR22## where R⁴ is hydrogen or an alkyl radical with one to nine carbon atoms.

There are amine curing agents on the market that are made from phenol, formalin (a water solution of formaldehyde) and a polyamine. These have no relationship to the urea-formaldehyde polyamines of the present invention because they are made by a different chemical route, and have vastly different properties. The manufacture of these phenol-formaldehyde amines is illustrated by product Data Sheet 22-E-370-2-6 published by Veba-Chemie AG of Germany, which describes the reacting of phenol and 36% formalin using a basic catalyst. The polyamine is added to this water solution of the phenol-formaldehyde resin, and subsequently the water is driven off, resulting in a yellow viscous liquid.

As stated earlier, this resin is in no way related to the urea-formaldehyde polyamines of this invention, for no ether groups are formed in the water solution of phenol and formaldehyde under the above-stated basic conditions.

The urea-formaldehyde ether monomers may be made in an alcohol medium. The urea, paraformaldehyde (a solid form or polymer of formaldehyde having typically 91% formaldehyde content), and an alcohol, such as methanol, are first subjected to basic conditions under low heat such as 50° C. This brief alkaline reaction causes the paraformaldehyde to dissolve. Then the reaction is made strongly acidic, e.g., a pH of 2; at this time an exotherm takes place, as a result of the formation of ether groups, for ethers of urea-formaldehyde are only formed under acid conditions. The reaction is held at 70°-80° C. for a time in the order of one hour, to insure good ether formation. The monomer reaction is then finished by bringing the pH to 7.0. Another method of making these N,N'-bis(alkoxy methyl) urea monomers is detailed in U.S. Pat. No. 3,309,341.

There may be small amounts of methylol groups in these urea-formaldehyde ether monomers. These methylol groups react with the polyamine in the same manner as the ethers react. ##STR23##

The formation of ether groups in the urea-formaldehyde resin can be followed by infrared spectrophotometry analysis. A sample of the reaction is scanned in an infrared spectroscopy instrument. The ether groups in urea-formaldehyde are shown by an infrared peak at 9.3 microns (1075 cm⁻¹). See the book An Infrared Spectroscopy Atlas for the Coatings Industry, 1980, Federation of Societies for Coating Technology, page 33.

This 9.3 micron peak develops soon after acidic conditions are made. The final urea-formaldehyde ether monomer has a very large 9.3 micron ether peak at the end of the reaction.

The progress of the reaction of the urea-formaldehyde ether monomer with the polyamine can be followed by noting that the ether peak is destroyed very soon after the urea-formaldehyde ether monomer is added to the polyamine. The finished reaction product has no trace of this 9.3 micron peak. The mixing of the urea-formaldehyde ether monomer into the polyamine is generally done at low temperature, such as 25° C. An exotherm takes place during the mixing which raises the temperature some 30° C. Then the alcohol and water of reaction are distilled off giving typically a water white, low viscosity, transparent liquid with remarkably good epoxy curing properties.

Some specific examples illustrate the formation of the urea-formaldehyde ether and related monomers and the reaction of the monomers with polyamines.

EXAMPLE 1 Urea-Formaldehyde Ether Monomer in Methanol

In a three liter glass flask fitted with a stainless steel paddle stirrer, thermometer, a pH electrode and a reflux condenser, is charged:

1200 g. methyl alcohol 99%

1200 g. 91% flake paraformaldehyde (corresponding to 1092 g. of 100% CH₂ 0=36.4 moles)

540 g. urea=9 moles.

This mix was stirred and heated to 40° C. The pH of this mix was 3.0. The pH was brought to 10.5 by the addition of a small amount of 40% sodium hydroxide. As the temperature rose to 55° C., the paraformaldehyde and the urea were dissolved, making a clear solution. At this point 50% H₂ SO₄ was added to bring the pH to 2.5. This caused a mild exotherm, bringing the temperature to 78° C. The pH was maintained at 2.0-2.5, and the temperature was maintained at about 80° C. for about forty minutes. Then the pH was brought to 7.0 with NaOH. The cooled urea-formaldehyde solution had suspended Na₂ SO₄ in it, which was filtered out leaving a water-white, transparent, low-viscosity liquid containing about 55% non-volatile urea-formaldehyde ether monomer. Infrared analysis showed a strong peak at 9.3 microns, indicating ethers of methylol groups.

EXAMPLE 2 Thiourea-Formaldehyde Ether Monomer in Methanol

It has been found that thiourea ##STR24## readily reacts in the same manner as urea in making the monomer.

In a 500 ml. flask fitted with a stainless steel paddle stirrer, thermometer, a pH electrode and reflux condenser, was charged:

One mole, 76 g. thiourea, crystals, 99%

Four moles, 132 g. 91% flake paraformaldehyde (corresponding to 120 g. of 100% CH₂ O) 200 g. methyl alcohol 99%.

This mix stirred and heated to about 40° C. The pH of this mix was 5.2. The pH was brought to 11.1 by the addition of a small amount of 40% sodium hydroxide. As the temperature rose to 60° C., the paraformaldehyde and thiourea dissolved making a clear solution. At this point 50% H₂ SO₄ was added to bring the pH to 2.5. This caused a mold exotherm bringing the temperature to 70° C. This mix was stirred for one hour maintaining the temperature at 65° to 70° C.

During this time the pH spontaneously fell to 1.65. Then the pH was brought to 7.0 with NaOH. The cooled thiourea-formaldehyde solution had suspended Na₂ SO₄ in it, which was filtered out leaving a water-white, transparent low-viscosity liquid containing about 48% non-volatile thiourea-formaldehyde ether monomer.

EXAMPLE 3 Composite Urea-Nonyl-Phenol Formaldehyde Ether Monomer

In a 500 ml. glass flask fitted with a stainless steel paddle stirrer, thermometer, pH electrode, and reflux condenser, the following ingredients were added:

0.5 mole, 110 g. nonyl phenol

0.5 mole, 30 g. urea

3.03 mole, (100 g. of 91% paraformaldehyde corresponding to 91 g. 100% CH₂ O) 250 g. isopropyl alcohol, 99%.

This mix was heated and stirred while 40% NaOH was added to bring the pH from 2.5 to 11.0. At 85° C. the paraformaldehyde and urea were dissolved to make a clear solution. Then 50% H₂ SO₄ was added to bring the pH to 1.2. A mold exotherm took place, causing some refluxing. The temperature was maintained at about 70° C. for an hour while the pH was held at or near 1.2. Then NaOH was used to bring the pH to 7.0. The filtered solution was a light yellow transparent solution containing about 47% urea-nonyl phenol formaldehyde ether monomer. A large infrared peak at 9.3 microns indicated ethers of methylol groups.

EXAMPLE 4 Composite Urea-Phenol Formaldehyde Ether Monomer

In a one liter glass flask fitted with a stainless steel paddle stirrer, thermometer, pH electrode and reflux condenser, the following ingredients were added:

300 g. methyl alcohol 99%

2 moles, 188 g. phenol, U.S.P.

1 mole, 60 g. urea

3 moles, 99g. 91% paraformaldehyde, (corresponding to 90 g. 100% CH₂ O).

The mix was stirred and heated while 40% NaOH was added to bring the pH from 6.5 to 9.5. At 50° C. the paraformaldehyde dissolved, forming a transparent, slightly yellow liquid. Then 50% H₂ SO₄ was added to bring the pH to 2.1. An exotherm took place, bringing the temperature from 52° to 68° C. The pH dropped to 1.0. The temperature was maintained at 64° C. for ten minutes and the pH was brought from 1.0 to 7.0 with NaOH.

The cooled solution had some white precipitate which was filtered off, leaving a water-white, transparent solution. Infrared analysis showed a strong urea carbonyl peak at 6.05 microns and a large ether peak at 9.3 microns. The solution had about 50% non-volatile urea-phenol formaldehyde ether monomer.

EXAMPLE 5 Urea-Formaldehyde Ether Monomer Reacted with an Aromatic Polyamine

The urea-formaldehyde ether monomer of Example 1, in an amount of 85 grams (47.5 grams of non-volatiles, i.e., 1 equivalents), is reacted with 1 mole (304 grams) of du Pont BABA, having a composition, weight percent:

    ______________________________________                                         p,p-methylene dianiline                                                                              3-10%                                                    2,4-bis(p-aminobenzyl) aniline                                                                      70-80%                                                    (triamine)                                                                     tetramine            10-80%                                                    higher amines        1.                                                        ______________________________________                                    

The aromatic polyamine was heated and stirred in a flask to 100° C. and the urea-formaldehyde ether monomer was added over 20 min. time and the temperature had climbed to 125° C.

Then 50 g. of benzyl alcohol was added to reduce the viscosity of this thick red brown liquid with a whitish crust on top. Methanol was distilled off during this time. Subsequently the whitish crust was dispersed in the red brown liquid and the crust dissolved into the main liquid giving a transparent viscous liquid at 150° C.

This liquid solidified as a dark red-brown brittle solid at about 90° C., considerably higher than the starting polymethylene dianiline. There was a urea carbonyl peak sown in infrared analysis of the final product at about 6.05 microns. This was not present in the starting polymethylene dianiline. The infrared peak at 6.05 microns indicated that a compound had been formed between the polymethylene dianiline and the urea-formaldehyde ether monomer.

Examples of the reaction of the urea-formaldehyde ether and related monomers with polyamines

All reactions were done in a glass flask fitted with paddle stirrer, thermometer, addition funnel and a distillation condenser. In all cases the polyamine was stirred in the flask at room temperature, while the urea-formaldehyde ether or related monomer solution in alcohol was added to the polyamine. If the opposite addition were done,--i.e., adding the polyamine to the urea-formaldehyde ether solution--a gel would result in a short time. A substantial exotherm results from the addition of the monomer solution etc. to the polyamine during the ten to twenty minutes addition time. Slow addition is important, for too-rapid addition can result in some gel particles.

After the addition of the monomer was complete, alcohol and water were distilled off from the urea-formaldehyde polyamine or related polyamine. Some distillations were at atmospheric pressure where the residue temperature was 130° C. Other distillations were done under reduced pressure of about 25 inches of vacuum where the temperature was 75° C.

In the following table urea-formaldehyde ether is abbreviated to UF, urea-formaldehyde ether monomer to UFM, and urea-phenol-substituted-formaldehyde ether to UPFM.

Note that in Example 7, the mole ratio of polyamine to UFM is about 2.66. Mole ratios much lower than about four result in formulations like this or similar to it, sometimes in mixtures with the four-to-one structure shown above: ##STR25##

                                      TABLE I                                      __________________________________________________________________________                                            Properties of the UF Polyamine          Example                                Color of     Viscosity at                                                                   25° C.              No.  UFM OR UPFM    Polyamine          Liquid       in Poises                  __________________________________________________________________________     6    130 g. UFM of Example 1                                                                       155 g. diethylene triamine                                                                        water white  1.2                             = 72g. non-volatile                                                                           1.5 moles          transparent                                  = 1.5 equivalents                                                         7    260 g. UFM of Example 1                                                                       206 g. diethylene triamine                                                                        water white  2.15                            = 143 g. non-volatile                                                                         2.0 moles          transparent                                  = 3 equivalents                                                           8    85 g. UFM of Example 1                                                                        146 g. triethylene tetramine                                                                      light yellow 2.4                             = 47.5 g. non-volatile                                                                        1.0 mole           transparent                                  = 1 equivalent                                                            9    167 g. UFM of Example 1                                                                       486 g. 70% solution of                                                                            water white transparent;                                                                    about 1                         = 92 g. non-volatile                                                                          hexamethylene diamine in H.sub.2 O                                                                when cooled to 15° C.,                = 1.93 equivalents                                                                            = 340 g. non-volatile                                                                             some white crystals                                         = 2.93 moles (Here there is                                                                       formed but melted at                                        excess which does not react                                                                       25° C.                                               with the UFM.)                                             10   260 g. UFM of Example 1                                                                       500 g. 70% solution of                                                                            water white  3.4                             = 144 g. non-volatile                                                                         hexamethylene diamine in H.sub.2 O                                                                transparent                                  = 3.04 equivalents                                                                            = 350 g. non-volatile                                                          = 3.20 moles                                               11   170 g. UFM of Example 1 = 95 g. non-volatile = 2.0                                                               water white transparent                                                                     1.8                        12   85 g. UFM of Example 1                                                                        230 g. Jeffamine D-230                                                                            very slightly yellow                                                                        3.3                             = 47.5 g. non-volatile                                                                        polyoxypropylene diamine                                                                          transparent                                  = 1 equivalent M W 230                                                    13   170 g. UFM of Example 1                                                                       122 g. monoethanol amine                                                                          light yellow 11.2                            = 95 g. non-volatile                                                                          = 2 moles (Note this usable                                                                       transparent                                  = 2 equivalents                                                                               (monoamine.)                                               14   200 g. UPFM of Example 3                                                                      164 g. 85% solution of                                                                            light yellow about 1.5                       urea-nonyl phenol                                                                             hexamethylene diamine in H.sub.2 O                                                                transparent                                  formaldehyde monomer                                                                          = 140 g. non-volatile                                           = 94 g. non-volatile                                                                          = 1.2 moles                                                     = 1.2 equivalents                                                         15   160 g. UPFM of Example 3                                                                      160 g. Adogen 572  light tan - yellow                                                                          1.1                             = 77 g. non-volatile                                                                          (oleyl diamine)    translucent                                  = 1.0 equivalent                                                                              = 1.0 equivalent                                           16   300 g. UPFM of Example 4                                                                      300 g. 70% solution of                                                                            light yellow about 1.5                       = 150 g. non-volatile                                                                         hexamethylene diamine in H.sub.2 O                                                                transparent                             17   65 g. UFM of Example 1 = 36 g. non-volatile = 0.75                                             ##STR26##         water-white sl. cloudy                                                                      10.8                       18   43 g. UFM of Example 1                                                                        300 g. Jeffamine ED-600                                                                           water white  11                              = 24 g. non-volatile                                                                          [poly(oxyethylene) diamine]                                                                       transparent                                  = 0.5 equivalent                                                                              mol. wt. 600                                               19   172 g. UFM of Example 1                                                                       340 g. isophorone diamine                                                                         water white  33                              =  95 g. non-volatile                                                                         = two moles        transparent                                  = 2 equivalents                                                                               a product of Huels,                                                            formerly Veba                                              20   172 g. UFM of Example 1                                                                       316 g. trimethyl   very light yellow                                                                           3.8                             = 95 g. non-volatile                                                                          hexamethylene diamine                                                                             transparent                                  = 2 equivalents                                                                               = two moles                                                                    a product of Huels,                                                            formerly Veba                                              21   85 g. UFM of Example 1                                                                        129 g. N--aminoethyl piperazine                                                                   water-white  3.15                            = 47.5 g. non-volatile                                                                        = one mole         transparent                                  = 1.0 equivalent                                                          22   130 g. UFM of Example 1                                                                       171 g. of water white                                                                             water white  3.0                             = 71 g. non-volatile                                                                          distillate prepared from du                                                                       transparent                                  = 1.5 equivalents                                                                             Pont DACH, a mixture of about                                                  half 1,2 diamine cyclohexane,                                                  about one-quarter hexamethy-                                                   lene diamine, and remainder                                                    of related compounds includ-                                                   ing 2-methyl pentamethylene                                                    diamine. The original material                                                 is very dark, but the distal-                                                  late is water white.                                       23   107 g. thiourea-formaldehyde                                                                  166 g. 70% hexamethylene                                                                          water-white  4.0                             monomer in methanol,                                                                          diamine in water   transparent                                  Example 2      = 116 g. 100% HMD                                               = 51.5 g. non-volatiles                                                                       = 1.0 mole                                                      = 1.0 equivalent                                                          24   85 g. UFM      136 g. m-xylene diamine                                                                           water-white  --                              = 47.5 g. non-volatile                                                                        = 1 mole           transparent                                  = 1 equivalent                                                            __________________________________________________________________________

Examples of cure of epoxy resins

The various urea-formaldehyde type polyamines were reacted with the standard epxoy resin--the diglycidyl ether of bisphenol A.

The curing reactions were all begun at room temperature, with the resulting exotherm uncontrolled.

The polyamine-to-epoxy-resin ratios shown in the examples below are only approximately stoichiometric and illustrate the curing ability of these new curing agents. For optimum results, one should vary the illustrated ratios in each instance and study the properties of the resulting films or castings, to arrive at the desired property or properties, or to achieve a desired compromise. These properties may be hardness, flexibility, chemical resistance, etc., obtaining either a maximum of one of these or the desired best overall aggregation of properties, for maximum results for one property does not necessarily mean maximum results for another property; so there may not be any one ratio at which the best results for all properties coincide.

                                      TABLE II                                     __________________________________________________________________________     Example                                                                             UF Polyamine                       Epoxy Curing                                                                               Properties of              No.  Per Example                                                                              Reactants and Proportions                                                                               Results     Cured                      __________________________________________________________________________                                                         Resin                      25   diethylene                                                                               30 g. - liquid epoxy resin                                                                              Clear transparent                                                                          Film on steel                   triamine  Dow DER 331              mix at once.                                                                               very tough                      Example 6 13 g. - curing agent of Example 6                                                                       Exothermed very hot                                                            in 40 minutes.                         26   diethylene                                                                               Same as 25 above.        Same as 25 above.                                                                          Same as 25 above,               triamine                                       but perhaps harder              Example 7                                      film                       27   triethylene                                                                              50 g. DER 331            Slightly cloudy                                                                            Very tough film                 tetramine 10 g. curing agent of Example 8                                                                         mix at once.                                Example 8                          Exotherm hot in                                                                40 minutes.                            28   hexamethylene                                                                            30 g. DER 331            Very transparent                            diamine   10 g. of curing agent                                                                              at 15° C.                                                                    mix at once.                                Example 9 of Example 9 amine       Exotherm very, very                                                            hot in 45 minutes.                     29   hexamethylene                                                                            Same as 28 above         Same as 28 above.                           diamine                                                                        Example 10                                                                30   polyoxypropylene                                                                         30 g. DER 331            Clear transparent                                                                          Excellent,                      diamine MW 400                                                                           15 g. curing agent of Example 11                                                                        mix. Mild exotherm                                                                         transparent                     Example 11                         in about 4 hours.                                                                          tough, fairly                                                                  flexible, glossy                                                               film.                      31   polyoxypropylene                                                                         30 g. DER 331            Transparent mix.                            diamine MW 230                                                                           15 g. curing agent of Example 12                                                                        Slow but positive                           Example 12                         cure at room                                                                   temperature.                           32   monoethanol amine                                                                        30 g. DER 331            Hazy mix, cured                                                                            Soft solid.                     Example 13                                                                               15 g. of curing agent of Example 13                                                                     in 24 hours                            33   hexamethylene                                                                            30 g. DER 331            Very hot exotherm                                                                          Excellent film                  diamine   15 g. of curing agent of Example 14                                                                     in 40 minutes                                                                              on steel.                       Example 14                                                                34   oleyl diamine                                                                            30 g. DER 331            Made transparent                            Example 15                                                                               30 g. of curing agent of Example 15                                                                     mix at once. Mix                                                               applied to steel                                                               panel under water.                                                             Film cured under                                                               water in 24 hours.                     35   hexamethylene                                                                            53 g. DER 331            Mix transparent                                                                            In 24 Hours the                 diamine   18 g. of curing agent                                                                              at 15° C.                                                                    once. Very hot exo-                                                                        film was glossy,                Example 16                                                                               of Example 16            therm in 35 minutes.                                                                       transparent and                                                    Applied to steel                                                                           very tough and                                                     panel. Set to solid                                                                        hard.                                                              film in 2 hours.                       36   polyoxypropylene                                                                         15 g. DER 331                                                        triamine MW 400                                                                          30 g. of curing agent                                                                              at 18° C.                                 Example 17                                                                               of Example 17                                                   37   poly (oxyethylene)                                                                       30 g. DER 331,           Very transparent                                                                           Very slow cure.                 diamine MW 600                                                                           20 g. of curing agent of Example 18                                                                     water-white mix                                                                            Formed at soft                  Example 18                         once.       asting in 10                                                                   days.                      38   isophorone                                                                               50 g. DER 331            Made transparent                            diamine   20 g. of curing agent of Example 19                                                                     mix at once. Water-                         Example 19                         white. Hot exotherm                                                            in 60 minutes.                         39   trimethyl 50 g. DER 331            Made transparent                            hexamethylene                                                                            20 g. of curing agent of Example 20                                                                     mix at once.                                diamine                            Exotherm of 70° C.                   Example 20                         in 90 minutes.                         40   N-amino ethyl                                                                            60 g. DER 331            Made transparent                                                                           Made hard film on               piperazine                                                                               30 g. of curing agent of Example 21                                                                     mix at once. Very                                                                          an aluminum panel.              Example 21                         hot exotherm in                                                                40 minutes.                            41   1,2 diamine                                                                              30 g. DER 331            Made transparent                                                                           Made hard film on               cyclohexane                                                                              15 g. of curing agent of Example 22                                                                     mix at once.                                                                               an aluminum panel.              Example 22                         Hot exotherm in                                                                40 minutes.                            42   2,4 bis   20 g. DER 331            Transparent dark                                                                           Made excellent                  (p-aminobenzl)                                                                           10 g. of curing agent of Example 5                                                                      brown-red liquid                                                                           hard transparent                aniline   5 g. benzyl alcohol      mixing, cured to                                                                           glossy adhesive                 Example 5                          hard casting in                                                                            film on steel and                                                  24 hours.   on aluminum in 24                                                              hours.                     43   hexamethylene                                                                            50 g. DER 331            Mix transparent                             diamine   20 g. of curing agent of Example 23                                                                     at once. Hot                                Example 23                         exotherm in 35                                                                 minutes.                               44   m-xylene  50 g. DER 331            Mix transparent                             diamine   20 g. of curing agent of Example 24                                                                     at once. Hot                                Example 24                         exotherm in 35                                                                 minutes.                               __________________________________________________________________________ 

The invention having been described and exemplified, what I claim as my invention is:
 1. ##STR27## where X¹ is ##STR28## and X² is X¹ or ##STR29## where R¹ is one of the following: ##STR30## x varying from about 2 to about 6 ##STR31## where X+Y+Z=5.3 ##STR32## where a+c=3.5 and b=13.5 ##STR33## (o) mixture of ##STR34## R² and R³ are both H where R¹ is any of (a) to (o) and when R¹ is (p), either R² or R³, but not both, is C₁₈ H₃₅, while the other is H, andR⁴ is H or an alkyl radical with one to nine carbon atoms.
 2. ##STR35## where X¹ is ##STR36## were R¹ is one of the following: ##STR37## x varying from about 2 to about 6 ##STR38## where X+Y+Z=5.3 ##STR39## where a+c=3.5 and b=13.5 ##STR40## (o) mixture of ##STR41## and R² and R³ are both H.
 3. ##STR42## where X¹ is ##STR43## and X² is ##STR44## where R¹ is one of the following: ##STR45## x varying from about 2 to about 6 ##STR46## where X+Y+Z=5.3 ##STR47## where a+c=3.5 and b=13.5 ##STR48## (o) mixture of ##STR49## R² and R³ are both H, and R⁴ is H or an alkyl radical with one to nine carbon atoms.
 4. ##STR50## where X¹ is ##STR51## and X² is X¹ or ##STR52## where R¹ is --CH₂ --CH₂ --CH₂, either R² or R³, but not both, being C₁₈ H₃₅, while the other is H, andR⁴ is H or an alkyl radical with one to nine carbon atoms.
 5. ##STR53## where R¹ is ##STR54##
 6. ##STR55## where R¹ is ##STR56##
 7. ##STR57## where R¹ is --CH₂ --CH₂ --CH₂ --CH₂ --CH₂ --CH₂ --.
 8. ##STR58## where R¹ is --CH(CH₃)--CH₂ --O--CH₂ --CH(CH₃)--X X varying from about 2 to about
 6. 9. ##STR59## where R¹ is R1 ? ##STR60## where X+Y+Z=5.3.
 10. ##STR61## where R¹ is ##STR62## where a+c=3.5 and b=13.5.
 11. ##STR63## where R¹ is ##STR64##
 12. ##STR65## where R¹ is ##STR66##
 13. ##STR67## where R¹ is ##STR68##
 14. ##STR69## where R¹ is ##STR70##
 15. ##STR71## where R¹ is ##STR72##
 16. ##STR73## where R¹ is ##STR74##
 17. ##STR75## where R¹ is ##STR76##
 18. ##STR77## where R¹ is ##STR78##
 19. ##STR79## where R¹ is a mixture of ##STR80##
 20. The non-gel reaction product ofabout two to about four moles of an aliphatic, cycloaliphatic, or aromatic polyamine with about one mole of a monomer of (a) urea-formaldehyde ether, (b) a phenolic substituted monomer of urea-formaldehyde ether, or (c) thiourea-formaldehyde ether, in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.
 21. The non-gel reaction product of about two to about four moles of an aliphatic polyamine with about one mole of a monomer of(a) urea-formaldehyde ether, (b) phenolic substituted urea-formaldehyde ether, or (c) thiourea-formaldehyde ether, in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.
 22. The non-gel reaction product of about two to about four moles of a cycloaliphatic polyamine withabout one mole of a monomer of (a) urea-formaldehyde ether, (b) phenolic substituted urea-formaldehyde ether, or (c) thiourea-formaldehyde ether, in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.
 23. The non-gel reaction product ofabout two to about four moles of an aromatic polyamine with about one mole of urea-formaldehyde ether monomer, in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.
 24. ##STR81##
 25. The reaction product of about four moles of monoethanol amine with one mole of a monomer of urea-formaldehyde ether. 